Process for the manufacture of metalcation-deficient zeolites



United States Patent 3,460,904 PROCESS FOR THE MANUFACTURE OF METAL- CATION-DEFICIENT ZEOLITES Dean Arthur Young, Yorba Linda, Calif., assignor to Union Oil Company of California, Los Angeles, Calif, a corporation of California N 0 Drawing. Continuation-impart of application Ser. No. 457,485, May 20, 1965. This application Jan. 15, 1968, Ser. No. 697,587 The portion of the term of the patent subsequent to May 14, 1985, has been disclaimer! Int. Cl. C011) 33/28 US. Cl. 23112 8 Claims ABSTRACT OF THE DISCLOSURE Zeolitic alkali metal cations are rapidly and efficiently exchanged out of crystalline, alumino-silicate zeolites by subjecting such zeolites to ion exchange with ammonium salt solutions containing, at least during the latter stages of the exchange treatment, sufficient added acid to maintain a pH between about 2 and 4.5 during the exchange.

RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 457,485, filed May 20, 1965, now US. Patent No. 3,383,169.

BACKGROUND AND SUMMARY OF THE INVENTION This invention relates to a novel method of preparing metal-cation-deficient molecular sieve zeolites. More particularly, this invention relates to an improved process for the preparation of the ammonium form of crystalline, zeolitic alumino-silicates of the molecular sieve type from acid-sensitive, alkali metal and/or alkaline earth metal zeolites by a novel ion-exchange procedure.

Briefly stated, the invention comprises ion-exchanging a substantial portion of the exchangeable metal cation of a crystalline, alumino-silicate zeolite having a SiO /Al O mole-ratio between about 2 and 6 with ammonium ions in the presence of sufficient hydrogen ions to maintain a pH below about 4.5, but above about 2.0. The invention further contemplates calcining the resulting ammonium zeolite at a temperature above about 600 F. for a sufficient length of time to effect thermal decomposition of the zeolitic ammonium ions, with resultant formation of a hydrogen and/or decationized molecular sieve zeolite. The ammonium ion-exchange procedures heretofore employed require extended, multi-stage contacting of the zeolite with large volumes of ammonium salt solutions if a substantially complete exchange is required. These exhaustive treatments are time-consuming and expensive, and the major object of this invention is to provide convenient, rapid and economical methods for achieving 90l00% exchange of ammonium ions for zeolitic metal cations such as sodium.

The preparation of metal-cation-deficient, aluminosilicate zeolites involves the replacement of the original zeolitie metal cations, particularly the alkali metal and alkaline earth metal cations, with hydrogen ions or their complete removal with resultant formation of a decationized zeolite. To these ends, it has recently been discovered (US. Patent No. 3,130,006) that certain silicarich zeolitic molecular sieves can be prepared in their ammonium form by ion-exchanging the initial zeolite, usually in a sodium form, with an ammonium salt solution. The ammonium form can then be decomposed at relatively high temperatures to produce a deammoniated zeolite which exhibits a high degree of crystallinity, high 3,460,904 Patented Aug. 12, 1969 surface area, and relatively high acidity. The procedures followed in this patent to remove the sodium cation include (1) ion-exchanging with unbuffered ammonium salts at pH values substantially greater than 4.5, and (2) acid extraction to form the hydrogen zeolite directly. The preferred method involves exhaustive, batch-wise ion-exchange procedures using large volumes of ammonium salt solutions. During the initial stage or stages of contacting, a considerable proportion of the original zeolitic sodium, e.g. 50-60% thereof, is readily exchanged, but as the exchange approaches completion, e.g. after 70-90% of the sodium has been removed, the remaining sodium is removed with great difficulty. Thus, even after extended multi-stage contacting, the zeolite still retains appreciable amounts of sodium. The acid extraction procedure is even less successful in effecting complete removal of sodium, usually removing less than half, unless strong acids are used which attack the zeolite framework, resulting in dissolution of the alumina and essential loss in zeolite crystallinity.

It has now been discovered that crystalline l00% ammonium zeolites may be' efficiently prepared from their sodium or other metal forms by the process of this invention, which comprises contacting an acid-sensitive, crystalline, alumino-silicate zeolite having a SiO /Al O mole-ratio between about 2 and 6 with an ammonium salt solution containing sufiicient added acid to maintain a pH between about 2.0 and 4.5, and preferably between about 2.5 and 4.0, during at least the latter stages of the ion-exchange treatment. It is within the contemplated scope of the invention to use either batch or contiglous treatment while still maintaining the desired pH range. Specifically, it is contemplated that the pH be maintained between 2.0 and 4.5 by the continuous or periodic addition of a mineral or organic acid. A weak acid such as acetic acid is preferred because of its greater buffering effect.

The zeolites contemplated herein comprise the acidsensitive molecular sieves, and are composed usually of silica, alumina, and one or more exchangeable cations such as sodium, magnesium, calcium, etc. They are further characterized by having a Slo /A1 0 mole-ratio between about 2.0 and 6.0, and crystal pores of relatively uniform diameter, usually between about 4 and 14 A. Suitable zeolites found in nature include for example analcite, chabazite, erionite, and faujasite. Suitable synthetic molecular sieve zeolites include, for example, those of the A, X, Y, and L crystal types, or synthetic forms of the natural zeolites noted above.

The naturally occurring crystalline zeolites are usually found in an alkaline earth metal form, or mixed alkaline earth-alkali metal forms. The synthetic molecular sieves normally are prepared first in the sodium or potassium forms. In their sodium form, the general formula for the preferred Y molecular sieve zeolites of this invention is expressed as follows:

i I A1203 1 WSlOgI JCH O where x=0 to about 9, and w=3 to about 6.

For use as a cracking base, or in other acid-catalyzed reactions, it is preferred that most or all of the original zeolitic monovalent metals be ion-exchanged out with ammonium ions followed by heating to decompose the zeolitic ammonium ions, leaving in their place hydrogen ions and/ or exchange sites which have actually been decationized by further removal of water:

A 11+ ,z z 1120 As to the final zeolite produced, there is some uncertainty as to whether the heating of the ammonium zeolite produces a hydrogen zeolite or a decationized (cation-deficient) zeolite, but it is clear that, (a) hydrogen zeolites are formed upon initial thermal decomposition of the ammonium zeolite, and (b) if true decationization does occur upon further heating of the hydrogen zeolites, the decantionized zeolite also passess desirable catalytic activity. Both of these forms, and the mixed forms, are designated herein as being metal-cation-deficient.

This invention is also useful in the manufacture of mixed hydrogen-polyvalent metal zeolites. Thus, the ammonium zeolite of this invention may be back-exchanged with metal salt solutions, preferably polyvalent metals such as magnesium, zinc, calcium, or rare earth metal salts, to prepare a mixed metal-ammonium zeolite which may then be calcined to form the mixed hydrogen-polyvalent metal zeolite.

If it is desired to use the foregoing zeolites as hydrocracking or isomerization catalysts, it is preferred to activate the same by incorporating a minor proportion of a suitable metal hydrogenating component, normally a Group V-I-B and/or Group VII metal. The preferred hydrogenating metals comprise the Group VIII noble metals, and particularly palladium, platinum or rhodium. Other specific promoters which may be employed include e.g., tungsten, molybdenum, chromium, manganese, etc. The quantity of such metals can vary within wide ranges. Generally, any amount between 0.1 percent and about 20 percent by weight may be used. -In the case of the noble metals, it is normally preferred to use about 0.2 percent to 2.0 percent by weight. The preferred method of adding the hydrogenating metal is by ion-exchange. This is accomplished by digesting the ammonium zeolite in an aqueous solution of a suitable compound of the desired metal wherein the metal is present in a cationic form, as described for example in Belgian Patent No. 598,686. The metal-ammonium zeolite may then be subjected to final calcining and activation in order to convert the remaining ammonium ions to hydrogen ions.

There are several different procedures by which the acid-sensitive zeolites can be converted to the metal-cationdeficient forms of this invention, two of the most practical methods being as follows:

Method 1: Continuous exchange.An acid, preferably a strong mineral acid, is added to an aqueous slurry of the sodium zeolite until the pH is between about 2.0 and 4.5. Then the slurry is charged to a filter press, or other suitable vessel having a porous support for the zeolite. An ammonium salt solution acidified with a Weak acid, e.g. ammonium nitrate and acetic acid, with a pH between 2.0 and 4.5, is percolated through the bed until the desired degree of replacement of sodium ions has occurred. Then the exchanged material is washed with dilute, e.g. 1%, aqueous ammonium hydroxide to remove traces of acid prior to drying or calcining. The metal-cation-deficient zeolite is thereafter prepared by heating to decompose the zeolitic ammonium ions.

Method 2: Batch exchange.The sodium zeolite is slurried with an aqueous ammonium salt solution. Sufficient strong mineral acid is gradually added to this slurry to maintain the pH between 2.0 and 4.5 during the following to 90 minutes. Then the slurry is filtered, the filter cake resuspended in ammonium nitrate, and acidified to a pH of '2 to 4.5 for the next exchange period. This procedure is repeated until the desired replacement of sodium ions has occurred. Then the zeolite is washed with aqueous ammonia, drained, dried and heated to decompose the ammonium ions, thereby forming a corresponding hydrogen, and/ or decationized zeolite.

The first of these methods is preferred, mainly because it provides for automatic control of pH throughout the length of the zeolite bed by virtue of using a weak buffering acid. Moreover, in the initial acidification,

where pH can be easily controlled by external mechanical means and kept uniform throughout the slurry, a strong mineral acid may be employed thereby reducing costs. But if a strong mineral acid is employed during the continuous exchange treatment, there will be a tendency to develop a large pH gradient in the zeolite bed, which makes for inefficiency.

In the second, or batch, method there is little advantage to be gained by using the more expensive weak acids, and hence strong mineral acids may be employed throughout, with the attendant disadvantages of multi-stage batch operations.

Either of the foregoing procedures can be modified without significant loss in efficiency by carrying out the initial portion of the exchange treatment in the absence of added acid at conventional pHs of e.g. 6-8, to remove e.g. 2580% of the original sodium. Acid is then aded to the ammonium salt solution to maintain the pH below about 4.5, preferably below 4.0, during the remainder of the exchange treatment. By far the greatest improvement in efi'iciency resulting from the acidified exchange treatment is obtained in the latter stages of the contacting, during which removal of the last 1030% of the total sodium to be removed is effected.

By these or other procedures contemplated herein the Na O content of the zeolite can easily be reduced to below about 3 percent by weight, preferably to between about 0 and 1.5 percent. This means that more than about to percent, and preferably at least about 90 to 99 percent of the zeolitic sodium is replaced with ammonium ions and/ or hydrogen ions, and this can be accomplished in times ranging from about 1 hour to 20 hours, without significant sacrifice of crystallinity.

Any other conventional liquid-solid contacting procedure is contemplated for the ammonium ion exchange. The essential requirement is to maintain the slurry within the stated pH ranges during at least the terminal stages of the exchange treatment by the continuous or intermittent addition of acid. Normally, the exchange is carried out at ambient room temperatures of e.g. 1530 C., but elevated temperatures of e.g. 50-150 C. are advantageous in hastening the reaction, as is the use of solutions which are fairly concentrated in ammonium salt, e.g. 515 molar. Examples of suitable ammonium salts include ammonium nitrate, ammonium chloride, ammonium sulfate, ammonium citrate, ammonium acetate, etc. Suitable acids include nitric, hydrochloric, sulfuric, acetic, formic, etc.

It has been found that weak acids are preferable to strong acids in the exchange step because the buffering elfect furnished by the weak acid counteracts the continuous alkaline reaction of the sodium zeolite. Sodium Y-zeolite in contact with an aqueous solution functions as a slowly hydrolyzing salt of a weak acid and a strong base. If a strong acid is employed during the ammonium ion exchange, the desired pH levels cannot be maintained without continuous, carefully controlled addition of incremental amounts thereof. By employing weak acids having a dissociation constant below about 10* a stoichiometric excess can be employed without lowering the pH below about 2.0, thus avoiding the necessity of carefully controlled continuous addition of acid. Suitable weak acids include phosphoric, formic, acetic, propionic, butyric, citric, tartaric, etc.

The following examples are cited to illustrate the invention, but are nOt to be construed as limiting in scope:

Example I To demonstrate the effect of pH on the completeness of exchange of sodium for ammonium ions, four S-gram samples of a sodium zeolite Y (9.2 Wt. percent Na O; 5.16 SiO /Al O mole-ratio; 93% crystallinity) were subjected to continuous ion exchange for 80-115 minutes at 95100 C., by percolating through each sample supported on a filter plate 200 ml. of a 20% ammonium nitrate solution to which varying amounts of ammonium hydroxide, nitric acid or acetic acid had been added in order to obtain the desired pH. The results were as follows:

1 As measured in effluent exchange liquor.

2 pH of this sample initially adjusted to 3.0 by sluirying in 20 ml. of water containing 5.7 ml. 01 17.4 N acetic acid (in order to overcome buffering effect of Na-Y sieve).

None of these treatments had any significant effect on crystallinity of the zeolite.

It is readily apparent that pH has a substantial effect on the completeness of exchange obtainable in a given number of stages. In fact, the ionic activity coefiicient of sodium in the Y-sieve appears to be proportional to the logarithm of the hydrogen ion concentration. However, this promoting effect of acid on the zeolitically bound sodium can only be utilized in the presence of a third cation such as ammonium, as shown in the following example:

Example II Two additional S-gram samples of the Na-Y sieve employed in Example I were adjusted to pH 3.0 by slurrying in aqueous acid, and then subjected to ion exchange as described in Example I with aqueous acid solutions free of ammonium ion. The results were as follows:

Obviously, direct acid treatment is relatively inefifective for removing zeolitic sodium.

Example 111 This example shows that acid-ammonium ion exchange also decreases the total quantity of ammonium salt solution required to effect a given degree of exchange. Two parallel, 3-stage batch exchanges were carried out, using in each case 200 grns. of a Na-Y molecular sieve having a SiO /Al O mole-ratio of 4.69 and a Na O content of 7.1%. In series G, the three exchanges were carired out with aqueous ammonium nitrate solutions. In series H, acetic acid was partially substituted for NH NO during the first exchange and completely substituted for NH NO during the second exchange. The total combined equivalents of NH NO +HOAc during the three exchanges was equal to the total equivalent of NH NO during the three exchanges of the G series. The results were as follows:

It is thus apparent that in series H, more sodium was removed with less ammonium salt than was required in series G.

Example IV This example illustrates a practical batch-exchange procedure using a weak acid to reduce the Na O content of a Y-sieve to below 1% by weight.

One hundred grams of an 89% crystalline, sodium Y molecular sieve containing 44.1% H 0 and 7.1% Na O (12.7% Na O on a dry basis) was first acidified by slurrying in 500 milliliters of distilled H O to which was added suflicient glacial acetic acid to give an initial pH of 2.8. The acidified zeolite was filtered oil, washed with Water and then subjected to four successive batch exchanges with acidified 1.0 molar ammonium nitrate solution, each batch containing 2.96 equivalents of ammonium nitrate (per equivalent of Na O originally present in the zeolite), and suflicient .added acetic acid to give an initial pH of 2.8 Each exchange consisted of heating the slurry to 90100 C. for 30 minutes followed by filtertering, and reslurrying. During each exchange the pH rose to about 3.4.

The exchanged zeolite was then washed in a 1% solution of NH OH, dried at C. for 16 hours, and calcined at 540 C. for 12 hours to remove water and de compose the ammonium ions. The resulting zeolite composition was then found to contain 0.37% by weight of residual Na O, calculated for a dry basis, indicating that about 97.1% of the original sodium had been replaced with ammonium ions and/or hydrogen ions.

Essentially the same result is obtained when the above procedure is modified by omitting the acid from the first ammonium nitrate exchange solution, whereby the first exchange is elfected in the pH range of about 5.5-7 Whether acid is added or not, the first exchange treatment removes about 4050% of the original sodium.

Example V Another four-batch exchange was carried out in the same manner as described in Example IV, except that nitric acid was employed throughout instead of acetic acid, and sufficient 1.0 molar ammonium nitrate solution was used in each exchange to provide 3.26 equivalents of ammonium nitrate per equivalent of Na O originally present in the zeolite. In this series, the pH of each exchange slurry rose from 2.8 to about 3.7 (instead of 3.4),

thus demonstrating the buffering eflFect of acetic acid.

In this case, even though a total of 13.0 equivalents of NH NO per equivalent of Na O was employed (as compared to 11.8 equivalents in Example IV), the final zeolite contained 0.81% Na O, indicating that about 93.6% of the original sodium had been replaced with ammonium.

It is not intended that the invention should be limited to the details described above since many variations may be made by those skilled in the art without departing from the scope or spirit of the following claims.

I claim:

1. A method for the manufacture of a crystalline ammonium zeolite of the molecular sieve type, which comprises first contacting an alkali metal alumino-silicate molecular sieve zeolite with an aqueous solution of an ammonium salt to effect a substantial but incomplete exchange of zeolitic alkali metal ions for ammonium ions at a pH above 4.5, and thereafter further contacting the resulting partially exchanged zeolite with a relatively more acidic aqueous ammonium salt solution containing sufiicient added acid to maintain a pH between about 2 and 4.5 during said further contacting, and continuing said further contacting until at least about 80% of the original alkali metal content of said alkali metal aluminosilicate molecular sieve zeolite has been removed by ion exchange.

2. A method as defined in claim .1 wherein said further contacting is carried out at a pH below 4.0.

3. A method as defined in claim 1 wherein said first contacting is continued for .a sufiicient time to remove 25-80% of the original alkali metal from said zeolite, and wherein at least about 10% of the total alkali metal removed is removed during said further contacting.

4. A method as defined in claim 1 wherein said molecular sieve zeolite is a sodium Y molecular sieve having a SiO /AI O mole-ratio between about 3 and 6.

5. A method as defined in claim 1 wherein said added acid is a weak acid having a dissociation constant below about l0- 6. A method as defined in claim 1 wherein said added acid is a strong acid having a dissociation constant above about 10 7. A method as defined in claim 1 wherein said first contacting is carried out at a pH above about 6.

8. A method as defined in claim 1 wherein said first contacting is carried out at a pH above about 6, and is continued for a sufficient time to remove 25-80% of the original alkali metal from said zeolite, and wherein at least about 10% of the total alkali metal removed is removed during said further contacting.

References Cited UNITED STATES PATENTS 4/1964 Rabo et al. 23-ll2 X 3,375,205 3/1968 Wadlinger et al. 252-455 3,383,169 5/1968 Young 23-112 EDWARD J. MEROS, Primary Examiner 

